The prior art has shown that compounds such as methyl o-hydroxycinnamate may be converted to coumarin by utilizing a thermal process in which the o-hydroxycinnamate may be heated to a temperature above 200.degree. C. for a relatively long period of time to convert the aforesaid methyl o-hydroxycinnamate to coumarin. However, when the products which were obtained from a phenol-methyl acrylate reaction and which comprise coumarin as well as methyl o-hydroxycinnamate were maintained at a temperature of 90.degree. C. in the absence of oxygen but without the addition of any catalyst, there was not a further conversion of the methyl o-hydroxycinnamate to coumarin. In contradistinction to this, when methyl o-hydroxycinnamate was treated with a catalyst of the type hereinafter set forth in greater detail at a temperature of 90.degree. C., there was a substantial conversion of the methyl o-hydroxycinnamate to coumarin with a substantial selectivity. Other prior art patents have shown that compounds such as m-aminophenol may be condensed with various acrylic acids in a Lewis acid-catalyzed reaction to form 7-aminocoumarins following oxidation by nitrobenzene compounds. However, as will hereinafter be shown in greater detail, it has now been discovered that by utilizing a catalyst which contains a metal of Group VIII of the Periodic Table, either in solid or soluble form, it is possible to convert o-hydroxycinnamates or o-hydroxycinnamic acids to coumarin compounds without having to use the strong acid catalysts such as the Lewis acids which have been utilized in the past. Likewise, the unexpected discovery that these compounds containing a metal of Group VIII of the Periodic Table can be used as catalysts to effect the conversion of the aforesaid compounds to coumarin compounds takes the present invention outside of the scope of the classical Perkin condensation reaction which also is effected in the presence of acid catalysts.
This invention relates to a process for the conversion of ortho-coumaric acids or ortho-coumarates to coumarins. More specifically, the invention relates to a process for converting these compounds which, in the present specification and appended claims, are also referred to as o-hydroxycinnamic acids and o-hydroxycinnamates to coumarins in the presence of certain catalytic compositions of matter, said catalyst containing a metal of Group VIII of the Periodic Table.
Coumarins which are organic compounds, some of which possess fragrant odors, may be used as deodorizing and odor-enhancing agents in cosmetics and toiletry articles such as perfumes, colognes, soaps, talcs, bath powders, or in other products such as tobacco, inks, rubbers, etc., where aromatic ingredients are required. Certain coumarin compounds, especially certain hydroxycoumarins, are fluorescent organic compounds which may be used as whiteners for cloth in laundry soaps, as sun-screen agents in skin care formulations, and as dyes useful in modulating electromagnetic energy outputs from laser equipment. These compounds may be prepared by trans-cis isomerization and lactonizaton reactions in which o-hydroxycinnamates or o-hydroxycinnamic acids of the type hereinafter set forth in greater detail are cyclized in the presence of certain catalytic compositions of matter.
It is therefore an object of this invention to provide a process for the conversion of certain o-hydroxycinnamates and o-hydroxycinnamic acids to coumarins.
In one aspect an embodiment of this invention resides in a process for the preparation of a coumarin which comprises contacting a reactive compound consisting essentially of an o-hydroxycinnamate, an o-hydroxycinnamic acid or a mixture thereof with a solid or liquid catalyst containing a metal of Group VIII of the Periodic Table at a temperature in the range of from about 25.degree. to about 200.degree. C. and a pressure in the range of from about atmospheric to about 100 atmospheres, and recovering the resultant coumarin.
A specific embodiment of this invention is found in a process for the preparation of a coumarin which comprises contacting methyl o-hydroxycinnamate with a catalyst comprising palladium composited on a carbon support at a temperature in the range of from about 25.degree. to about 200.degree. C. and a pressure in the range of from about atmospheric to about 100 atmospheres, and recovering the resultant coumarin.
Other objects and embodiments will be found in the following further detailed description of the present invention.
As hereinbefore set forth the present invention is concerned with a process for converting ortho-coumarates (o-hydroxycinnamates) or ortho-coumaric acids (o-hydroxycinnamic acids) to coumarin compounds which are important industrial chemicals. Conversions of the starting materials are effected by treating said materials at conversion conditions in the presence of a catalyst comprising a compound containing a metal of Group VIII of the Periodic Table. The conversion conditions which are employed to effect the reactions of the present invention will include temperatures in the range of from about 25.degree. up to about 200.degree. C. and preferably in a range of from about 25.degree. (ambient) to about 180.degree. C. While in the preferred embodiment of the invention the conversion reactions are effected at pressures ranging from atmospheric up to about 20 atmospheres, it is also contemplated that superatmospheric pressures ranging up to about 100 atmospheres or more may be employed. When utilizing superatmospheric pressures, the pressures are afforded by the introduction of a substantially inert gas such as nitrogen into the reaction zone, the particular amount of pressure which is used being that which is necessary to maintain a major portion of the reactants in the liquid phase.
Examples of o-hydroxycinnamates (ortho-coumarates) or o-hydroxycinnamic acids (ortho-coumaric acids) which may be converted to coumarins according to the process of this invention will include those compounds having the formula: ##STR1## in which n ranges from 0 to 4, R is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkaryl, aralkyl, hydroxyl, alkyloxy, cycloalkyloxy, aryloxy, alkaryloxy, aralkyloxy, carboxyl, cyano, fluoro, chloro, bromo, iodo, amino, alkylamino, cycloalkylamino, arylamino, alkarylamino, aralkylamino, nitro, nitroso, amide, formyl, acetyl, propionyl, butyroyl, benzoyl, and vinyl radicals and R' is selected from the group consisting of hydrogen, alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals. Some specific examples of these compounds will include o-hydroxycinnamic acid, alkyl coumarates in which the alkyl group, R', will contain from 1 to about 4 carbon atoms such as methyl o-hydroxycinnamate, ethyl o-hydroxycinnamate, n-propyl o-hydroxycinnamate, isopropyl o-hydroxycinnamate, n-butyl o-hydroxycinnamate, t-butyl o-hydroxycinnamate, n-amyl o-hydroxycinnamate, etc.; aryl o-hydroxycinnamates such as phenyl o-hydroxycinnamate, naphthyl o-hydroxycinnamate, anthracyl o-hydroxycinnamate, etc,; cycloalkyl o-hydroxycinnamates such as cyclopentyl o-hydroxycinnamate, cyclohexyl o-hydroxycinnamate, methylcyclopentyl o-hydroxycinnamate, cycloheptyl o-hydroxycinnamate, etc.; alkaryl o-hydroxycinnamates such as o-tolyl o-hydroxycinnamate, m-tolyl o-hydroxycinnamate, p-tolyl o-hydroxycinnamate, o-ethylphenyl o-hydroxycinnamate, m-ethylphenyl o-hydroxycinnamate, p-ethylphenyl o-hydroxycinnamate, etc.; aralkyl o-hydroxycinnamates such as benzyl o-hydroxycinnamate, o-methylbenzyl o-hydroxycinnamate, m-methylbenzyl o-hydroxycinnamate, p-methylbenzyl o-hydroxycinnamate, etc.; ring-substituted o-hydroxycinnamic acids and ring-substituted o-hydroxycinnamates such as 3 -(2'-hydroxy-3'-methylphenyl)acrylic acid, 3-(2'-hydroxy-4'-methylphenyl)-acrylic acid, 3-(2'-hydroxy-5'-methylphenyl)-acrylic acid, 3-(2'-hydroxy-6'-methylphenyl)-acrylic acid, 3-(2'-hydroxy-3',4'-dimethylphenyl)-acrylic acid, methyl 3-(2'-hydroxy-3',5'-dimethylphenyl)-acrylate, ethyl 3-(2'-hydroxy-3',6' -dimethylphenyl)-acrylate, n-propyl 3-(2'-hydroxy-4',5'-diethylphenyl)-acrylate, t-butyl 3-(2'-hydroxy-4', 5',6'-trimethoxyphenyl)-acrylate, cyclohexyl 3-(2'-hydroxy-3',4',5',6'-tetramethylphenyl)-acrylate, methyl 3-(2',3'-dihydroxyphenyl)-acrylate, methyl 3-(2',5'dihydroxyphenyl)acrylate, ethyl 3-(2',4',6'-trihydroxyphenyl)-acrylate, isopropyl 3-(2'-hydroxy-5'-phenylphenyl)-acrylate, phenyl 3-(2'-hydroxy-4'-carbomethoxyphenyl)-acrylate, naphthyl 3-(2'-hydroxy-6'-cyanophenyl)-acrylate, methyl 3-(2'-hydroxy-4',5' -methylenedioxyphenyl)-acrylate, methyl 3-(2'-hydroxy-5'-aminophenyl)-acrylate, sec-butyl 3-(2'-hydroxy-4'-chlorophenyl)-acrylate, etc.; vinyl-substituted o-hydroxycinnamic acids and o-hydroxycinnamates such as 2-methyl-3-(2'-hydroxyphenyl)-acrylic acid, 3-methyl-3-(2'-hydroxyphenyl)-acrylic acid, 2,3-dimethyl-3-(2'-hydroxyphenyl)-acrylic acid, 2-ethyl-3-(2'-hydroxyphenyl)-acrylic acid, 2-methyl-3-(2',5'-dihydroxyphenyl)-acrylic acid, methyl 2-methyl-3-(2'-hydroxyphenyl)acrylate, ethyl 2-phenyl-3-(2'-hydroxy-5'-methylphenyl)-acrylate, n-propyl 2-benzyl-3-(2'-hydroxyphenyl)-acrylate, methyl 2-p-tolyl-3-(2'-hydroxyphenyl)-acrylate, etc. It is to be understood that these compounds are only representative of the class of o-hydroxycinnamates and 0075 may be converted to coumarins and that the present invention is not necessarily limited thereto.
The catalytic compositions of matter which are to be employed to effect the process of the present invention will comprise a compound containing a metal of Group VIII of the Periodic Table. In the preferred embodiment of the invention that catalyst will be in solid form, some specific examples of these catalysts being platinum composited on a solid support such as platinum composited on alumina, platinum composited on silica, platinum composited on a carbon support such as charcoal, platinum composited on a diatomaceous earth, platinum composited on an aluminosilicate such as faujasite, mordenite, etc., platinum metal, palladium composited on alumina, palladium composited on silica, palladium composited on charcoal, palladium composited on a diatomaceous earth, palladium composited on an aluminosilicate, palladium powder, the corresponding nickel, cobalt, iron, ruthenium, rhodium, osmium and iridium metals composited on alumina, silica, carbon, diatomaceous earth, aluminosilicates, etc. While as hereinbefore set forth, in the preferred embodiment of the invention, the catalyst is in solid form, it is also contemplated within the scope of this invention that soluble salts containing a metal of Group VIII of the Periodic Table may also be used, although not necessarily with equivalent results. Some specific examples of these soluble Group VIII metal salts which may be used will include platinum chloride, platinum nitrate, platinum acetate, platinum acetylacetonate, palladium chloride, palladium nitrate, palladium acetate, palladium acetylacetonate, nickel chloride, nickel nitrate, nickel acetate, nickel acetylacetonate, cobalt chloride, cobalt nitrate, cobalt acetate, cobalt acetylacetonate, etc. It is to be understood that the aforementioned catalysts, both solid and soluble in nature, are only representative of the class of compounds which may be employed to effect the reaction, and that the present invention is not necessarily limited thereto.
The process of the present invention involving the conversion of a compound of the type hereinbefore set forth in greater detail to a coumarin or coumarins may be effectd in any suitable manner and may comprise either a batch or continuous type of operation. For example, when a batch type operation is used, a quantity of the compound which is to undergo conversion is placed in an appropriate apparatus. In the event that the reaction is to be effected at atmospheric pressure this apparatus may comprise a flask equipped with appropriate stirring and reflux equipment. Alternatively, if the reaction is to be effected under superatmospheric conditions the apparatus will comprise a pressure-resistant piece of equipment such as an autoclave of the rotating or mixing type. If so desired, a substantially inert organic solvent such as n-pentane, n-hexane, n-heptane, cyclopentane, cyclohexane, cycloheptane, methylcyclopentane, benzene, toluene, the xylenes, phenol, acetic acid, propionic acid, etc., may also be present in the reaction zone. The reaction apparatus is then pressured to the desired operating pressure by means of a substantially inert gas such as nitrogen, if superatmospheric pressures are to be employed, and heated to the desired operating temperature in the range hereinbefore set forth. After maintaining the apparatus and contents thereof at this temperature for a predetermined period of time which may range from about 0.5 up to about 16 hours or more in duration, heating is discontinued. The apparatus and contents thereof are allowed to return to room temperature, any excess pressure if present is vented and the reaction mixture is recovered therefrom. The reaction mixture is then subjected to conventional means of separation and purification including filtration, washing, drying, extraction, fractional distillation, etc., whereby the desired product comprising a coumarin or coumarins is separated and recovered.
It is also contemplated within the scope of this invention that the process for converting a compound of the type hereinbefore set forth to a coumarin or coumarins may be effected in a continuous manner of operation. When such a type of operation is employed, the starting material comprising the compound is continuously charged to a reaction vessel containing the particular catalyst and which is maintained at the proper operating conditions of temperature and pressure. After being maintained in the apparatus for a predetermined period of time, the reactor effluent is continuously withdrawn and subjected to separation steps similar in nature to those hereinbefore set forth whereby the desired coumarin(s) is (are) separated and recovered while any unreacted starting materials are recycled to the reaction zone to form a portion of the feed stock. Inasmuch as the catalyst, in the preferred form, is solid in nature the continuous method of operation may be effected in several ways. One type of operation which may be employed constitutes a fixed bed method in which the catalyst is disposed in the reactor as a fixed bed and the starting materials are passed through said bed in either an upward or downward flow. Another type of operation which may be used constitutes the moving bed type of operation in which the catalyst and the reactant are passed through the reaction zone either concurrently or countercurrently to each other. Yet another type of operation which may be used is the slurry type of operation in which the catalyst is carried into the reaction zone as a slurry in the reactant. In each type of operation the reactor effluent is continuously withdrawn and treated in a manner similar to that hereinbefore set forth whereby the desired product is recovered and the reactant starting material is recycled to the reaction zone to form a portion of the feed stock therein.
The following examples are given to illustrate the process of the present invention. However, these examples are not intended to limit the generally broad scope of the present invention in strict accordance therewith.